CN107428875B

CN107428875B - Spray-dried catalyst composition, method of preparation and use in olefin polymerization processes

Info

Publication number: CN107428875B
Application number: CN201680013503.XA
Authority: CN
Inventors: R·B·潘内尔; M·D·阿韦
Original assignee: Univation Technologies LLC
Current assignee: Univation Technologies LLC
Priority date: 2015-03-10
Filing date: 2016-03-10
Publication date: 2021-02-26
Anticipated expiration: 2036-03-10
Also published as: WO2016145179A1; CA2978925C; BR112017019133A2; BR112017019133B1; CA2978925A1; ES2852023T3; SG11201707037TA; US20180051111A1; EP3268399A1; EP3268399B1; CN107428875A; US10414843B2

Abstract

Methods of preparing supported catalyst compositions using spray drying are disclosed. The supported catalyst composition is used in olefin polymerization.

Description

Spray-dried catalyst composition, method of preparation and use in olefin polymerization processes

Technical Field

The present disclosure relates to spray-dried catalyst compositions, methods of making the same, and their use in processes for polymerizing olefins. In particular, the present disclosure relates to spray-dried catalyst compositions comprising methylalumoxane and a metallocene-type catalyst and/or a conventional-type transition metal catalyst.

Background

The polyolefin industry has in recent years focused primarily on the development of new catalysts that provide new and improved products. Transition metal catalysts, such as, for example, metallocene catalysts, are currently widely used to make polyolefin polymers, such as polyethylene polymers. Transition metal catalysts generally require an activator or cocatalyst in order to achieve a commercially acceptable level of activity. Exemplary activators include Methylaluminoxane (MAO) and molecular activators, or cocatalysts such as Lewis acid boranes.

Furthermore, for use in particle-forming polymerization processes, such as gas phase processes, the transition metal catalyst is typically supported on a particulate support. Typically, the supported transition metal catalysts are employed in the form of free-flowing powders, requiring vacuum drying of the supported catalyst during manufacture in order to remove the liquid diluent from which the catalyst is prepared. On a commercial scale where the bulk size of the supported catalyst may be about 200kg solids or greater, the vacuum drying step can be extremely time consuming, especially when relatively high boiling liquids, such as toluene, must be removed. WO 99/26989 describes the preparation of supported metallocene catalysts in batch sizes of about 550kg, wherein the catalyst is prepared in toluene and subsequently dried under vacuum for at least 15 hours. WO 99/61486 describes the preparation of supported metallocene catalysts which likewise have a batch size of about 550kg, the catalyst being dried under vacuum for 15 hours. The long drying times have a significant negative impact on catalyst manufacturing economics.

It is therefore desirable to provide a lower cost process for preparing supported transition metal catalysts on a large scale, which also provides a catalyst that can be operated in a polymerization process with good yields.

Disclosure of Invention

The present disclosure provides a lower cost process for preparing a supported catalyst composition for olefin polymerization, wherein the process provides a faster way to dry large quantities of the supported catalyst composition without altering the catalyst performance. In one aspect, there is provided a process for making a supported catalyst composition for olefin polymerization, the process comprising the steps of:

a) forming a suspension comprising one or more porous particulate supports, one or more activator compounds and one or more catalyst compounds in one or more liquid diluents; and

b) spray drying the suspension to form a supported catalyst composition;

wherein step b) is performed at a rate sufficient to produce at least 200kg of the supported catalyst composition in 10 hours or less. The spray drying step allows for large scale rapid drying of the suspension formed in step a) to produce a supported catalyst composition with overall shorter batch process times.

Step b) may be carried out at a rate sufficient to produce at least 200kg of the supported catalyst composition in a time of 9 hours or less, or 8 hours or less, or 7 hours or less, or 6 hours or less, or 5 hours or less, or 4 hours or less, or 3 hours or less.

The formation of the suspension in step a) may be carried out in a time of 9 hours or less, or 8 hours or less, or 7 hours or less, or 6 hours or less, or 5 hours or less, or 4 hours or less, or 3 hours or less.

The supported catalyst composition can have a residual liquid content after spray drying of 10 wt.% or less, or 7 wt.% or less, or 5 wt.% or less, or 4 wt.% or less, or 3 wt.% or less, or 2 wt.% or less.

Step b) may be carried out at a rate sufficient to produce at least 300kg, or at least 400kg, or at least 500kg of the supported catalyst composition in 10 hours or less.

One advantage of the disclosed process is that drying the supported catalyst composition to an acceptably low residual diluent content can be achieved in a significantly shorter time than with conventional vacuum drying processes.

For example, a supported catalyst composition having a batch size (total solids content) of about 550kg may be spray dried from a toluene suspension in about 5 hours. This can be compared to a drying time of about 15 hours using conventional vacuum drying.

The time taken for step a) may be substantially the same as the time taken for step b). The difference between the time spent in step a) and the time spent in step b) may be within 2 hours. The difference between the time spent in step a) and the time spent in step b) may be within 1 hour.

Additionally and unexpectedly, the supported catalyst compositions prepared by the disclosed methods can have comparable or higher activity in olefin polymerization than catalyst compositions prepared by conventional vacuum drying methods.

The weight% of the solids of the suspension in the liquid diluent may be between about 5 weight% and about 60 weight%, or between about 10 weight% and about 50 weight%, or between about 20 weight% and about 40 weight%.

The suspension may be spray dried at a rate of between about 100kg/h and 1000kg/h or between about 200kg/h and about 800 kg/h.

The porous particulate support may comprise particulate group 2, group 3, group 4, group 5, group 13, and group 14 oxides or chlorides. The porous particulate support may comprise particulate silica. The porous particulate support may be dehydrated at elevated temperatures.

The porous particulate support may have an average particle size in the range of from about 0.1 to about 500 μm, or from about 1 to about 200 μm, or from about 1 to about 50 μm, or from about 5 to about 50 μm.

The one or more activator compounds may comprise an organometallic compound. The one or more activator compounds may comprise an alumoxane or a neutral or ionic stoichiometric activator. The one or more activator compounds may comprise methylalumoxane or modified methylalumoxane.

The liquid diluent may comprise an aliphatic or aromatic hydrocarbon. The liquid diluent may comprise toluene.

The one or more catalyst compounds may comprise titanium, zirconium or hafnium atoms. The supported catalyst composition can comprise two or more catalyst compounds comprising titanium, zirconium, or hafnium atoms.

The catalyst compound may comprise:

(pentamethylcyclopentadienyl) (propylcyclopentadienyl) MX₂，

(Tetramethylcyclopentadienyl) (propylcyclopentadienyl) MX₂，

(Tetramethylcyclopentadienyl) (butylcyclopentadienyl) MX₂，

Me₂Si (indenyl)₂MX₂，

Me₂Si (tetrahydroindenyl)₂MX₂，

(n-propylcyclopentadienyl)₂MX₂，

(n-butylcyclopentadienyl)₂MX₂，

(1-methyl, 3-butylcyclopentadienyl)₂MX₂，

HN(CH₂CH₂N(2,4,6-Me₃Phenyl))₂MX₂，

HN(CH₂CH₂N(2,3,4,5,6-Me₅Phenyl))₂MX₂，

(propylcyclopentadienyl) (tetramethylcyclopentadienyl) MX₂，

(butylcyclopentadienyl))₂MX₂，

(propylcyclopentadienyl)₂MX₂And mixtures thereof,

wherein M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH₂SiMe₃And C₁To C₅An alkyl or alkenyl group.

The method may comprise any one or more of the above disclosed features in any combination.

In another aspect there is provided a supported catalyst composition for the polymerization of olefins, the composition being formed by any of the above disclosed processes.

In another aspect, there is provided a process for polymerizing olefins, the process comprising:

contacting olefins in a reactor under polymerization conditions with one or more supported catalyst compositions prepared by any of the methods as disclosed above to produce olefin polymers or copolymers

Detailed Description

Before the present compounds, components, compositions, and/or methods are disclosed and described, it is to be understood that this invention is not limited to particular compounds, components, compositions, reactants, reaction conditions, ligands, transition metal compounds, or the like, unless otherwise specified, as such can vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

It must also be noted that, as used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to "a halogen atom" as in a moiety "substituted with a halogen atom" includes more than one halogen atom, such that the moiety may be substituted with two or more halogen atoms, reference to "a substituent" includes one or more substituents, reference to "a ligand" includes one or more ligands, and the like.

As used herein, all references to periodic tables and groups thereof are to the NEW NOTATION (NEW NOTATIONs) published in the "hough brief CHEMICAL DICTIONARY", Thirteenth Edition, John Wiley & Sons (HAWLEY' S CONDENSED CHEMICAL DICTIONARY, third Edition, John Wiley & Sons, Inc.), (1997) (copied under the IUPAC permit), unless reference is made to the previous IUPAC form labeled with roman numbers (also appearing therein), or unless otherwise indicated.

Disclosed herein are advantageous processes for preparing supported catalyst compositions for polymerizing olefins. The process is characterized in that it utilizes spray drying as a step in the preparation of the catalyst. The supported catalyst composition can be prepared in a much shorter time relative to the previously described methods and can be operated continuously in a polymerization process with good yields.

Catalyst and process for preparing same

Any catalyst or combination of catalysts for polymerizing olefins is suitable for use in the process of the present disclosure. The following is a discussion of various catalysts set forth for purposes of explanation and not limitation.

General definitions

As used herein, a "supported catalyst composition" includes one or more catalyst compounds for polymerizing olefins and at least one activator, or at least one cocatalyst, and at least one support. The supported catalyst composition can include any suitable number of catalyst compounds in any combination as described herein and any activator or co-catalyst in any combination as described herein. The "supported catalyst composition" may also contain one or more additional components known in the art to reduce or eliminate reactor fouling, such as continuity additives.

As used herein, "catalyst compound" may include any compound capable of catalyzing the polymerization or oligomerization of an olefin upon activation, wherein the catalyst compound comprises at least one group 3 to group 12 atom and optionally at least one leaving group bonded thereto.

Conventional catalyst

Conventional catalysts are those conventional Ziegler-Natta (Ziegler-Natta) catalysts and Phillips-type (Phillips-type) chromium catalysts well known in the art. Examples of conventional types of transition metal catalysts are disclosed in U.S. Pat. nos. 4,115,639, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741. Conventional types of transition metal catalyst compounds that may be used in the present invention include, but are not limited to, transition metal compounds from groups III to VIII of the periodic table of elements.

These conventional types of transition metal catalysts can be represented by the formula: MR_xWherein M is a group IIIB to VIII, preferably a group IVB metal, more preferably titanium; r is halogen or alkoxy; and x is the valence state of the metal M. Non-limiting examples of R may include alkoxy, phenoxy, bromide, chloride, and fluoride. Conventional types of transition metal catalysts wherein M is titanium may include, but are not limited to, TiCl₄、TiBr₄、Ti(OC₂H₅)₃Cl、Ti(OC₂H₅)Cl₃、Ti(OC₄H₉)₃Cl、Ti(OC₃H₇)₂Cl₂、Ti(OC₂H₅)₂Br₂、TiCl₃.1/3AlCl₃And Ti (OC)₁₂H₂₅)Cl₃。

Transition metal catalyst compounds of the conventional type based on magnesium/titanium electron-donor complexes suitable for use in the present invention are described, for example, in U.S. Pat. nos. 4,302,565 and 4,302,566. MgTiCl₆(Ethyl acetate)₄Derivatives are one such example. British patent application 2,105,355 describes various conventional types of vanadium catalyst compounds. Non-limiting examples of conventional types of vanadium catalyst compounds include vanadyl trihalides, vanadyl alkoxyhalides, and vanadyl alkoxides, such as VOCl₃、VOCl₂(OBu) (where Bu ═ butyl) and VO (OC)₂H₅)₃(ii) a Vanadium tetrahalides and alkoxy halides, e.g. VCl₄And VCl₃(OBu); vanadium and vanadyl acetoacetates and vanadyl chloroacetoacetonates, e.g. V (AcAc)₃And VOCl₂(AcAc) wherein (AcAc) is acetylPyruvate radical. An example of a conventional type of vanadium catalyst compound is VOCl₃、VCl₄And VOCl₂- -OR, wherein R is a hydrocarbyl group, preferably C₁To C₁₀Aliphatic or aromatic hydrocarbon groups such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, naphthyl, etc.; and vanadium acetylacetonate.

Conventional types of chromium catalyst compounds (commonly referred to as Phillips-type catalysts) suitable for use in the present invention may include CrO₃Chromocene, silyl chromate, chromium oxychloride (CrO)₂Cl₂) Chromium 2-ethyl-hexanoate, chromium acetyl acetonate (Cr (AcAc)₃) And the like. Non-limiting examples are disclosed in, for example, U.S. patent nos. 3,242,099 and 3,231,550.

Still other conventional types of transition metal catalyst compounds and catalyst systems suitable for use in the present invention are disclosed in U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566 and 5,763,723, and in published EP-A20416815A 2 and EP-A10420436. Transition metal catalysts of the conventional type according to the invention may also have the general formula M'₁M"X_2tY_uE, wherein M' is Mg, Mn and/or Ca; t is a number from 0.5 to 2; m' is a transition metal Ti, V and/or Zr; x is halogen, preferably Cl, Br or I; y may be the same or different and is halogen (alone or in combination with oxygen), -NR₂-OR, -SR, -COOR OR-OSOOR, wherein R is a hydrocarbyl group, in particular an alkyl, aryl, cycloalkyl OR aralkyl group, an acetylacetonate anion in an amount such as to satisfy the valency of M'; u is a number from 0.5 to 20; e is an electron donor compound selected from the following classes of compounds: (a) esters of organic carboxylic acids; (b) an alcohol; (c) an ether; (d) an amine; (e) esters of carbonic acid; (f) a nitrile; (g) phosphoramides, (h) esters of phosphoric and phosphorous acids and (j) phosphorus oxychloride. Non-limiting examples of complexes conforming to the above formula include: MgTiCl₅.2CH₃COOC₂H₅、Mg₃Ti₂Cl₁₂7CH₃COOC₂H₅、MgTiCl₅.6C₂H₅OH、MgTiCl₅.100CH₃OH、MgTiCl₅Tetrahydrofuran, MgTi₂Cl₁₂7C₆H₅CN、MgTi₂Cl₁₂6C₆H₅COOC₂H₅、MgTiCl₆2CH₃COOC₂H₅、MgTiCl₆6C₅H₅N、MgTiCl₅(OCH₃)2CH₃COOC₂H₅、MgTiCl₅N(C₆H₅)₂3CH₃COOC₂H₅、MgTiBr₂Cl₄2(C₂H₅)O、MnTiCl₅4C₂H₅OH、Mg₃V₂Cl₁₂.7CH₃COOC₂H₅、MgZrCl₆4 tetrahydrofuran. Other catalysts may include cationic catalysts, such as AlCl₃And other cobalt and iron catalysts well known in the art.

The conventional type transition metal catalyst compounds disclosed herein may be activated with one or more of the conventional types of promoters described below.

Conventional cocatalyst and other Components

The conventional type of cocatalyst compounds used for the above conventional type of transition metal catalyst compounds may be represented by the formula M³M⁴ _v X² _c R³ _b-cIs represented by the formula, wherein M³Is a metal of group IA, group IIA, group IIB and group IIIA of the periodic Table of the elements; m⁴Is a group IA metal of the periodic Table of the elements; v is a number from 0 to 1; each X²Is any halogen; c is a number from 0 to 3; each R³Is a monovalent hydrocarbon group or hydrogen; b is a number from 1 to 4; and wherein b minus c is at least 1. Other conventional types of organometallic co-catalyst compounds for use in the above conventional types of transition metal catalysts have the formula M³R³ _kWherein M is³Is a group IA, IIA, IIB or IIIA metal, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium and gallium; k is equal to 1,2 or 3, depending on M³The valence of which in turn is generally dependent on M³The number of the specific family; and each R³May be any monovalent hydrocarbon group.

Examples of conventional types of organometallic co-catalyst compounds of group IA, group IIA and group IIIA that can be used with the conventional types of catalyst compounds described above include, but are not limited to, methyllithium, butyllithium, dihexylmercuric, butylmagnesium, diethylcadmium, benzylpotassium, diethylzinc, tri-n-butylaluminum, diisobutylethylboron, diethylcadmium, di-n-butylzinc and tri-n-pentylboron, and specifically, alkylaluminum such as trihexylaluminum, triethylaluminum, trimethylaluminum and triisobutylaluminum. Other conventional types of promoter compounds may include mono-organic halides and hydrides of group IIA metals and mono-or di-organic halides and hydrides of group IHA metals. Non-limiting examples of such conventional type co-catalyst compounds may include diisobutylaluminum bromide, isobutyl dichloride, methylmagnesium chloride, ethylberyllium chloride, ethylcalcium bromide, diisobutylaluminum hydride, methylchloride, diethylboron hydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride, butylzinc hydride, boron dichlorohydride, aluminum dibromohydride, and cadmium bromohydride. Organometallic co-catalyst compounds of conventional type are known to those skilled in the art and a more complete discussion of these compounds can be found in U.S. Pat. Nos. 3,221,002 and 5,093,415.

Metallocene catalyst

Metallocene catalysts may include "half sandwich" compounds (i.e., at least one ligand) and "full sandwich" compounds (i.e., at least two ligands) having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bonded to at least one group 3 to group 12 metal atom and one or more leaving groups bonded to at least one metal atom. Hereinafter, these compounds will be referred to as "metallocenes" or "metallocene catalyst compounds".

The one or more metallocene catalyst compounds may be represented by formula (I): cp^ACp^BMX_n (I)

As described throughout the specification and claims, the metal atom "M" of the metallocene catalyst compound may be selected from the group consisting of group 3 to group 12 atoms and lanthanum group atoms; selected from the group consisting of group 4, group 5, and group 6 atoms; ti, Zr, Hf atoms or Zr. The group bonded to the metal atom "M" is such that the compounds described below in formulas and structures are neutral unless otherwise indicated. The Cp ligand(s) form at least one chemical bond with the metal atom M to form a "metallocene catalyst compound". The Cp ligands differ from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions.

M is as described above; each X is chemically bonded to M; each Cp group is chemically bonded to M; and n is 0 or an integer from 1 to 4, or 1 or 2.

From Cp in formula (I)^AAnd Cp^BThe ligands represented may be the same or different cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, either or both of which may contain heteroatoms and either or both of which may be substituted by a group R. Cp^AAnd Cp^BMay be independently selected from the group consisting of: cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.

Independently, each Cp of formula (I)^AAnd Cp^BMay be unsubstituted or substituted with any one or combination of substituents R. Non-limiting examples of substituents R as used in structure (I) include hydrogen radicals, hydrocarbyl radicals, lower hydrocarbyl radicals, substituted hydrocarbyl radicals, heterohydrocarbyl radicals, alkyl radicals, lower alkyl radicals, substituted alkyl radicals, heteroalkyl radicals, alkenyl radicals, lower alkenyl radicals, substituted alkenyl radicals, heteroalkenyl radicals, alkynyl radicals, lower alkynyl radicals, substituted alkynyl radicals, heteroalkynyl radicals, alkoxy radicals, lower alkoxy radicals, aryloxy radicals, hydroxy radicals, alkylthio radicals, lower alkylthio radicals, arylthio radicals, sulfoxy radicals, aryl radicals, substituted aryl radicals, heteroaryl radicals, aralkyl radicals, aralkylene radicals, alkaryl radicals, alkaryls, halides, haloalkyl radicals, haloalkenyl radicals, haloalkynyl radicals, heteroalkyl radicals, heterocycles, heteroaryl radicals, heteroatom-containing radicals, silyl radicals, boron radicals, phosphino radicals, phosphine radicals, amino radicals, amines, cycloalkyl radicals, acyl radicals, aroyl radicalsAlkyl thiols, dialkylamines, alkylamido, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl-and dialkyl-carbamoyl, acyloxy, acylamino, aroylamino, and combinations thereof.

More specific non-limiting examples of alkyl substituents R associated with formula (i) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all isomers thereof, such as tert-butyl, isopropyl, and the like. Other possible groups include substituted alkyl and aryl groups such as, for example, fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbyl-substituted organometalloid groups including trimethylsilyl, trimethylgermyl, methyldiethylsilyl, and the like; and halocarbon-substituted organometalloid radicals including tris (trifluoromethyl) silyl, methylbis (difluoromethyl) silyl, bromomethyldimethylgermyl, and the like; and disubstituted boron radicals including, for example, dimethylboron; and disubstituted group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, dimethylsulfide and diethylsulfide. Other substituents R include olefins such as, but not limited to, ethylenically unsaturated substituents including vinyl terminated ligands such as 3-butenyl, 2-propenyl, 5-hexenyl and the like. Two adjacent R groups, when present, may be joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of: carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, and combinations thereof. In addition, a substituent R group, such as 1-butyl, may form a bonding association with the element M.

Each X in formula (I) may be independently selected from the group consisting of: any leaving group, such as halide, hydride, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyAlkylthio, lower alkylthio, arylthio, sulfoxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, amine, cycloalkyl, acyl, aroyl, alkylthiol, dialkylamine, alkylamido, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl-and dialkyl-carbamoyl, acyloxy, acylamino, aroylamino, and combinations thereof. X can also be C₁To C₁₂Alkyl radical, C₂To C₁₂Alkenyl radical, C₆To C₁₂Aryl radical, C₇To C₂₀Alkylaryl group, C₁To C₁₂Alkoxy radical, C₆To C₁₆Aryloxy radical, C₇To C₁₈Alkylaryloxy radical, C₁To C₁₂Fluoroalkyl radical, C₆To C₁₂Fluoroaryl and C₁To C₁₂Heteroatom-containing hydrocarbons and substituted derivatives thereof. X is also selected from hydride, halide, C₁To C₆Alkyl radical, C₂To C₆Alkenyl radical, C₇To C₁₈Alkylaryl group, C₁To C₆Alkoxy radical, C₆To C₁₄Aryloxy radical, C₇To C₁₆Alkylaryloxy radical, C₁To C₆Alkyl carboxylic acid ester, C₁To C₆Fluorinated alkyl carboxylic acid esters, C₆To C₁₂Aryl carboxylic acid esters, C₇To C₁₈Alkyl aryl carboxylate, C₁To C₆Fluoroalkyl radical, C₂To C₆Fluoroalkenyl and C₇To C₁₈A fluoroalkyl aryl group. X may also be selected from hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoyloxy, tosyl, fluoromethyl and fluorophenyl. X is selected from C₁To C₁₂Alkyl radical, C₂To C₁₂Alkenyl radical, C₆To C₁₂Aryl radical, C₇To C₂₀Alkylaryl, substituted C₁To C₁₂Alkyl, substituted C₆To C₁₂Aryl, substituted C₇To C₂₀Alkylaryl and C₁To C₁₂Alkyl containing hetero atoms, C₁To C₁₂Aryl containing hetero atoms and C₁To C₁₂A heteroatom-containing alkylaryl group; chloride, fluoride, C₁To C₆Alkyl radical, C₂To C₆Alkenyl radical, C₇To C₁₈Alkylaryl, halogenated C₁To C₆Alkyl, halogenated C₂To C₆Alkenyl and halogenated C₇To C₁₈An alkylaryl group. X may be selected from fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyls (monofluoromethyls, difluoromethyls and trifluoromethyls) and fluorophenyls (monofluorophenyls, difluorophenyls, trifluorophenyls, tetrafluorophenyls and pentafluorophenyl).

The metallocene catalyst compounds and/or components may include those of formula (I) wherein Cp^AAnd Cp^BAre bridged to each other by at least one bridging group (a) such that the structure is represented by formula (II): cp^A(A)Cp^BMX_n (II)

These bridged compounds represented by formula (II) are referred to as "bridged metallocenes". Cp^A、Cp^BM, X and n are as defined above for formula (I); and wherein each Cp ligand is chemically bonded to M, and (a) is chemically bonded to each Cp. Non-limiting examples of bridging group (A) include divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent lower alkynyl, divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkylthio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl, divalent alkarylene, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocycle, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbon group, divalent lower alkyl, divalent lower alkynyl, divalent heteroalkenyl, divalent heterocycle, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbon group, divalent lower alkyl, divalent heteroalkenyl, divalentHydrocarbyl, divalent substituted hydrocarbyl, divalent heterohydrocarbyl, divalent silyl, divalent boroxy, divalent phosphino, divalent phosphine, divalent amino, divalent amine, divalent ether, divalent thioether. Additional non-limiting examples of bridging group a include divalent hydrocarbon groups containing at least one group 13 to group 16 atom, such as (but not limited to) at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, and tin atom, and combinations thereof; wherein the heteroatom may also be C substituted to satisfy neutral valency₁To C₁₂Alkyl or aryl. The bridging group (a) may also contain substituents R as defined above for formula (I), including halogen groups and iron. A more specific non-limiting example of bridging group (A) is represented by C₁To C₆Alkylene, substituted C₁To C₆Alkylene, oxygen, sulfur, R'₂C═、R'₂Si═、─Si(R')₂Si(R'₂)─、R'₂Ge ═, R 'P ═ (wherein "═" represents two chemical bonds), wherein R' is independently selected from the group consisting of: hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometallics, halocarbyl-substituted organometallics, disubstituted boron, disubstituted group 15 atoms, substituted group 16 atoms, and halogen groups; and wherein two or more R' may be linked to form a ring or ring system. The bridged metallocene catalyst compound of formula (II) may have two or more bridging groups (a).

Other non-limiting examples of bridging group (A) include methylene, ethylene (ethylene/ethylidene), propylene, isopropylene, diphenylmethylene, 1, 2-dimethylethylene, 1, 2-diphenylethylene, 1,2, 2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis (trifluoromethyl) silyl, di (n-butyl) silyl, di (n-propyl) silyl, di (isopropyl) silyl, di (n-hexyl) silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di (t-butylphenyl) silyl, di (p-tolyl) silyl and the corresponding moieties in which the Si atom is replaced by a Ge or C atom, Dimethylsilyl, diethylsilyl, dimethylgermyl and diethylgermyl.

The bridging group (A) may also be cyclic, comprising, for example, 4 to 10,5 to 7 ring members. The ring members may be selected from the elements described above, or from one or more of B, C, Si, Ge, N and O. Non-limiting examples of ring structures that may be present as or part of the bridging moiety are cyclobutyl, cyclopentyl, cyclohexylidene, cycloheptylidene, cyclooctylidene, and the corresponding rings wherein one or two carbon atoms are replaced by at least one of Si, Ge, N, and O, specifically, Si and Ge. The arrangement of bonds between the ring and the Cp groups may be cis, trans, or a combination.

The cyclic bridging group (a) may be saturated or unsaturated and/or carry one or more substituents and/or be fused to one or more other ring structures. If present, the one or more substituents may be selected from the group consisting of hydrocarbyl (e.g., alkyl, such as methyl) and halo (e.g., F, Cl). The one or more Cp groups which may optionally be fused to the above cyclic bridging moiety may be saturated or unsaturated and are selected from the group consisting of those having 4 to 10, more specifically 5,6 or 7 ring members selected from the group consisting of C, N, O and S such as, for example, cyclopentyl, cyclohexyl and phenyl. Furthermore, these ring structures may be fused to themselves, for example in the case of naphthyl. Furthermore, these (optionally fused) ring structures may carry one or more substituents. Illustrative non-limiting examples of such substituents are hydrocarbyl groups (especially alkyl groups) and halogen atoms.

Ligands Cp of the formulae (I) and (II)^AAnd Cp^BMay be different from each other or the same as each other.

The metallocene catalyst compound may comprise a single ligand metallocene compound (e.g. a monocyclopentadienyl catalyst component) as described, for example, in WO 93/08221, which is incorporated herein by reference.

The at least one metallocene catalyst compound may be an unbridged "half-sandwich" metallocene represented by formula (IV):

Cp^AMQ_qX_n (IV)

wherein Cp^AAs defined for the Cp group in (I) and is a ligand bound to M; each Q is independently bonded to M; q is also bonded to Cp^A(ii) a X is a leaving group as described in (I); n is in the range of 0 to 3, or 1 or 2; q is in the range of 0 to 3, or 1 or 2. Cp^AMay be selected from the group consisting of: cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted forms thereof, and combinations thereof.

In formula (IV), Q is selected from the group consisting of: ROO^-、RO-、R(O)-、-NR-、-CR₂-、-S-、-NR₂、-CR₃、-SR、-SiR₃、-PR₂-H and substituted and unsubstituted aryl, wherein R is selected from the group consisting of: hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxy, alkylthio, lower alkylthio, arylthio, sulfoxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, oxyboronyl, phosphino, phosphine, amino, amine, cycloalkyl, acyl, aroyl, alkylthiol, dialkylamine, alkylamido, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl-carbamoyl, and dialkyl-carbamoyl, Acyloxy, acylamino, aroylamino, and combinations thereof. R is selected from C₁To C₆Alkyl radical, C₆To C₁₂Aryl radical, C₁To C₆Alkylamine, C₆To C₁₂Alkylaryl amine, C₁To C₆Alkoxy and C₆To C₁₂An aryloxy group. Non-limiting examples of Q include C₁To C₁₂Carbamates, C₁To C₁₂Carboxylic acid esters (e.g. pivalate), C₂To C₂₀Allyl and C₂To C₂₀Heteroallyl moieties。

Described in another way, the above "half-sandwich" metallocenes may be as described in formula (II), as described for example in US 6,069,213:

Cp^AM(Q₂GZ)X_nor T (Cp)^AM(Q₂GZ)X_n)_m (V)

M, Cp therein^AX and n are as defined above;

Q₂GZ forms a multidentate ligand unit (e.g., pivalate) in which at least one of the Q groups forms a bond with M, and is defined such that each Q is independently selected from the group consisting of-O-, -NR-, -CR₂-and-S-; g is carbon or silicon; and Z is selected from the group consisting of R, -OR, -NR₂、-CR₃、-SR、-SiR₃、-PR₂And hydrides, with the proviso that when Q is-NR-, then Z is selected from the group consisting of-OR, -NR-₂、-SR、-SiR₃、-PR₂A group of compounds; and with the proviso that the neutral valency of Q is satisfied by Z; and wherein each R is independently selected from the group consisting of: hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxy, alkylthio, lower alkylthio, arylthio, sulfoxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, oxyboronyl, phosphino, phosphine, amino, amine, cycloalkyl, acyl, aroyl, alkylthiol, dialkylamine, alkylamido, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl-carbamoyl, and dialkyl-carbamoyl, Acyloxy, acylamino, aroylamino, and combinations thereof. R may be selected from the group consisting of: c₁To C₁₀Heteroatom-containing radical, C₁To C₁₀Alkyl radical, C₆To C₁₂Aryl radical, C₆To C₁₂Alkylaryl group, C₁To C₁₀Alkoxy and C₆To C₁₂An aryloxy group;

n can be 1 or 2;

t is selected from the group consisting of C₁To C₁₀Alkylene radical, C₆To C₁₂Arylene and C₁To C₁₀Heteroatom containing group and C₆To C₁₂A bridging group from the group consisting of heterocyclic groups; wherein each T group bridges adjacent "Cp^AM(Q₂GZ)X_nA "group, and chemically bonded to Cp^AA group;

m may be an integer of 1 to 7; or m may be an integer from 2 to 6.

The metallocene catalyst compounds may more specifically be described in structures (VIa), (VIb), (VIc), (VId), (VIe), and (VIf):

wherein in structures (VIa) through (VIf), M is selected from the group consisting of group 3 through group 12 atoms, from the group consisting of group 3 through group 10 atoms, from the group consisting of group 3 through group 6 atoms, from the group consisting of group 4 atoms, from the group consisting of Zr and Hf, or is Zr; wherein Q in (VIa) to (VIf) is selected from the group consisting of hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxy, alkylthio, lower alkylthio, arylthio, sulfoxy, aryl, substituted aryl, heteroaryl, arylalkyl, alkylaryl, alkarylyl, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing groupGroups, silyl groups, boroxy groups, phosphino groups, phosphines, amino groups, amines, cycloalkyl groups, acyl groups, aroyl groups, alkylthiols, dialkylamines, alkylamido groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, alkyl-and dialkyl-carbamoyl groups, acyloxy groups, acylamino groups, aroylamino groups, olefins, aryl groups, arylene groups, alkoxy groups, aryloxy groups, amines, arylamine (e.g., pyridyl) alkylamines, phosphines, alkylphosphines, substituted alkyl groups, substituted aryl groups, substituted alkoxy groups, substituted aryloxy groups, substituted amines, substituted alkylamines, substituted phosphines, substituted alkylphosphines, carbamates, heteroallyls, formates (non-limiting examples of suitable carbamates and formates include pivaloate, methyl acetate, p-methylbenzoate, benzoate, Diethyl carbamate and dimethyl carbamate), fluorinated alkyl groups, fluorinated aryl groups, and fluorinated alkyl carboxylates; wherein the saturated group defining Q may contain 1 to 20 carbon atoms; and wherein the aromatic group may contain from 5 to 20 carbon atoms; wherein R may be selected from the group consisting of divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent lower alkynyl, divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkylthio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl, divalent alkarylene, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocycle, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbon group, divalent lower hydrocarbon group, divalent substituted hydrocarbon group, divalent heterohydrocarbon group, divalent silyl group, divalent oxyboronyl group, divalent alkoxy-substituted alkyl group, divalent lower alkyl group, divalent alkoxy group, divalent lower alkoxy group, divalent aryloxy group, divalent alkylthio group, divalent lower alkylthio group, divalent arylthio group, divalent aryl group, divalent substituted aryl group, divalent, Divalent phosphine groups, divalent phosphines, divalent amino groups, divalent amines, divalent ethers, divalent thioethers. In addition, R may be from the group of divalent hydrocarbylene and heteroatom-containing hydrocarbylene, selected from the group consisting of alkylene, substituted alkylene and heteroatom-containing hydrocarbylene, selected from the group consisting of C₁To C₁₂Alkylene, or a mixture thereof,C₁To C₁₂Substituted alkylene and C₁To C₁₂A heteroatom-containing alkylene group or selected from the group consisting of C₁To C₄Alkylene groups. The two R groups may be identical in structure (VIf).

A is as described above for (A) in structure (II), and more specifically is selected from the group consisting of-O-, -S-, -SO-by a chemical bond₂-、-NR-、═SiR₂、═GeR₂、═SnR₂、─R₂SiSiR₂─、RP═、C₁To C₁₂Alkylene, substituted C₁To C₁₂Alkylene, divalent C₄To C₁₂Cyclic hydrocarbons and substituted and unsubstituted aryl groups; or is selected from C₅To C₈Cyclic hydrocarbon, -CH₂CH₂-、═CR₂And ═ SiR₂A group of compounds; wherein R is selected from the group consisting of: alkyl, cycloalkyl, aryl, alkoxy, fluoroalkyl, and heteroatom-containing hydrocarbons; r is selected from the group consisting of: c₁To C₆Alkyl, substituted phenyl, phenyl and C₁To C₆An alkoxy group; or R is selected from the group consisting of: methoxy, methyl, phenoxy, and phenyl; or a may be absent, in which case each R is as for R¹-R¹³Defining; each X is as described in (I) above; n is an integer from 0 to 4 or 1 to 3, or 1 or 2; and R is¹To R¹³Independently selected from the group consisting of: hydrogen radicals, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxy, alkylthio, lower alkylthio, arylthio, sulfoxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, oxyboronyl, phosphino, phosphine, amino, amine, cycloalkyl, acyl, aroyl, substituted aryl, heteroarylalkyl, heteroaryl, amino, cycloalkyl, acyl, aryl, heteroaryl, amino, alkoxy, substituted aryl, hydroxyl, alkylthio, aryl, and heteroaryl,Alkyl thiols, dialkylamines, alkylamido, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl-and dialkyl-carbamoyl, acyloxy, acylamino, aroylamino. To R¹³Can also be independently selected from C₁To C₁₂Alkyl radical, C₂To C₁₂Alkenyl radical, C₆To C₁₂Aryl radical, C₇To C₂₀Alkylaryl group, C₁To C₁₂Alkoxy radical, C₁To C₁₂Fluoroalkyl radical, C₆To C₁₂Fluoroaryl and C₁To C₁₂Heteroatom-containing hydrocarbons and substituted derivatives thereof; selected from the group consisting of: hydrogen radical, fluorine radical, chlorine radical, bromine radical, C₁To C₆Alkyl radical, C₂To C₆Alkenyl radical, C₇To C₁₈Alkylaryl group, C₁To C₆Fluoroalkyl radical, C₂To C₆Fluoroalkenyl radical, C₇To C₁₈A fluoroalkyl aryl group; or hydrogen, fluoro, chloro, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, phenyl, 2, 6-dimethylphenyl and 4-tert-butylphenyl; wherein adjacent R groups may form a saturated, partially saturated, or fully saturated ring.

The structure of the metallocene catalyst component represented by (VIa) may take various forms as disclosed in, for example, US 5,026,798, US 5,703,187 and US 5,747,406, including dimeric or oligomeric structures as disclosed in, for example, US 5,026,798 and US 6,069,213.

For the metallocene represented in (VId), R₁And R₂Forming a conjugated 6-membered carbocyclic ring system which may or may not be substituted.

The metallocene catalyst compounds described above are expected to include structural or optical or enantiomeric isomers (racemic mixtures) thereof, or may be pure enantiomers.

As used herein, a single, bridged, asymmetrically substituted metallocene catalyst compound having a racemic and/or meso isomer does not itself constitute at least two different bridged metallocene catalyst compounds.

The "metallocene catalyst compound" may comprise any combination of the features described above.

Metallocene compounds and catalysts are known in the art and any one or more may be utilized herein. Suitable metallocenes include, but are not limited to, all of the metallocenes disclosed and referenced in the above-listed U.S. patents as well as those disclosed and referenced in U.S. patent nos. 7,179,876, 7,169,864, 7,157,531, 7,129,302, 6,995,109, 6,958,306, 6,884748, 6,689,847, 2007/0055028 and published PCT applications nos. WO 97/22635, WO 00/699/22, WO 01/30860, WO 01/30861, WO 02/46246, WO 02/50088, WO 04/026921 and WO 06/019494, all of which are incorporated herein by reference in their entirety. Additional catalysts suitable for use herein include those referenced in U.S. patent nos. 6,309,997, 6,265,338, 2006/019925 and the following articles: chemical review (Chem Rev)2000,100,1253, lesconi (Resconi); chemical review 2003,103,283; european journal of chemistry (Chem Eur. J.)2006,12,7546 Mitsui; journal of molecular catalysis A (J Mol Catal A)2004,213,141; chemistry and Physics of macromolecules (Macromol Chem Phys),2005,206,1847; and American society of chemistry (J Am Chem Soc)2001,123,6847.

Containing group 15 catalysts

The supported catalyst composition may include one or metallocene catalysts as described above and/or other conventional polyolefin catalysts, as well as catalysts containing group 15 atoms described below.

A "group 15 atom containing" catalyst or a "group 15 containing" catalyst can include a complex of group 3 to group 12 metal atoms in which the metal atoms are 2 to 8 coordinated, one or more coordinating moieties including at least two group 15 atoms, and up to four group 15 atoms. The group 15 containing catalyst component may be a complex of a group 4 metal and from one to four ligands such that the group 4 metal is at least 2 coordinated, the coordinating moiety or moieties including at least two nitrogens. Representative group 15 containing compounds are disclosed in, for example, WO 99/01460, EP a 10893454, U.S. patent nos. 5,318,935, 5,889,128, 6,333,389B 2 and 6,271,325B 1.

The group 15 containing catalyst component may include group 4 imino-phenol complexes, group 4 bis (amide) complexes, and group 4 pyridyl amide complexes, which may activate the polymerization of olefins to any degree.

The group 15 containing catalyst component may Comprise HN (CH)₂CH₂N(2,4,6-Me₃Phenyl))₂MX₂And HN (CH)₂CH₂N(2,3,4,5,6-Me₅Phenyl))₂MX₂Wherein M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH₂SiMe₃And C₁To C₅An alkyl or alkenyl group.

The group 15 containing catalyst component may include bisamide compounds, such as [ (2,3,4,5,6 Me)₅C₆)NCH₂CH₂]₂NHZrBz₂。

Mixed catalyst

Additionally, one type of catalyst compound described above can be combined with another type of catalyst compound described herein by one or more activators or activation methods described below.

It is further contemplated that other catalysts may be combined with the metallocene catalyst compounds described herein. See, for example, U.S. patent nos. 4,937,299, 4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241.

Additionally, one or more metallocene catalyst compounds or catalyst systems may be used in combination with one or more conventional types of catalyst compounds or catalyst systems. Non-limiting examples of hybrid catalysts and catalyst systems are described in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031 and PCT publication WO 96/23010, published on 8/1/1996.

It is further contemplated that two or more conventional types of transition metal catalysts may be combined with one or more conventional types of promoters. Non-limiting examples of mixed conventional-type transition metal catalysts are described in, for example, U.S. Pat. Nos. 4,154,701, 4,210,559, 4,263,422, 4,672,096, 4,918,038, 5,198,400, 5,237,025, 5,408,015, and 5,420,090.

Activator for catalyst compound and activation method

An activator is broadly defined as any combination of agents that increases the rate at which a transition metal compound oligomerizes or polymerizes an unsaturated monomer (e.g., an olefin). The catalyst compound may be activated for oligomerization and/or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and/or polymerization.

Additionally, the activator may be a Lewis base (Lewis-base), such as, for example, diethyl ether, dimethyl ether, ethanol, or methanol. Other activators that may be used include those described in WO 98/07515, such as tris (2,2' -nonafluorobiphenyl) fluoroaluminate.

Combinations of activators may be used. For example, alumoxanes and ionizing activators may be used in combination, see, e.g., EP-B10573120, WO 94/07928 and WO 95/14044, and U.S. Pat. Nos. 5,153,157 and 5,453,410. WO 98/09996 describes the activation of metallocene catalyst compounds with perchlorates, periodates and iodates (including their hydrates). WO 98/30602 and WO 98/30603 describe the use of lithium (2,2' -biphenyibistrimethylsilicic acid) 4THF as an activator for metallocene catalyst compounds. WO 99/18135 describes the use of organoboron-aluminum activators. EP-B1-0781299 describes the use of silylium (silylium) salts together with noncoordinating compatible anions. WO 2007/024773 suggests the use of activator-supports which may comprise chemically treated solid oxides, clay minerals, silicate minerals or any combination thereof. Furthermore, activation methods such as the use of radiation (see EP-B1-0615981), electrochemical oxidation, and the like are also contemplated as activation methods for the purpose of bringing a neutral metallocene catalyst compound or precursor to a metallocene cation capable of polymerizing olefins. Other activators or methods for activating metallocene catalyst compounds are described in, for example, U.S. patent nos. 5,849,852, 5,859,653 and 5,869,723 and PCT WO 98/32775.

Alumoxanes also serve as activators in catalyst compositions. Aluminoxanes are generally oligomeric compounds containing- -Al (R) - -O- -subunits, where R is an alkyl group. Examples of the aluminoxane include Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, especially when the abstractable ligand is a halide. Mixtures of different aluminoxanes and modified aluminoxanes may also be used. For further description, see U.S. Pat. nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, and EP 0561476 a1, EP 0279586B 1, EP 0516476A, EP 0594218 a1, and WO 94/10180.

Aluminoxanes can be produced by hydrolysis of the corresponding trialkylaluminum compounds. MMAO can be produced by hydrolysis of trimethylaluminum and higher trialkylaluminum (e.g., triisobutylaluminum). MMAO is generally more soluble in aliphatic solvents and more stable during storage. There are ｃA variety of methods for preparing aluminoxanes and modified aluminoxanes, non-limiting examples of which are described in, for example, U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 3 and 5,939,346, and European publications EP-A-0561476, EP-B1-9586, EP-A-0594 and WO 858945, and WO 82 99/15534. Visually clear methylaluminoxane may be used. The cloudy or gelled aluminoxane can be filtered to produce a clear solution or the clear aluminoxane can be decanted from the cloudy solution. Another aluminoxane is Modified Methylaluminoxane (MMAO) cocatalyst type 3A (which is commercially available under the trade name Modified methylaluminoxane type 3A from Aksu chemical company (Akzo Chemicals, Inc.) and is disclosed in U.S. Pat. No. 5,041,584).

Ionizing or stoichiometric activators (neutral or ionic) may also be used, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenylboron-based metal precursor or a trisperfluoronaphthylboron-based metal precursor, a polyhalogenated heteroborane anion (see, e.g., WO 98/43983), boric acid (see, e.g., U.S. patent No. 5,942,459), or combinations thereof. Neutral or ionic activators may be used alone or in combination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators may include trisubstituted boron, tellurium, aluminum, gallium, and indium or mixtures thereof. The three substituents may each be independently selected from the group consisting of alkyl, alkenyl, halogen, substituted alkyl, aryl halide, alkoxy, and halide. The three substituents may be independently selected from the group: halogen, mono-or polycyclic (including halo-substituted) aryl, alkyl, and alkenyl compounds and mixtures thereof; or an alkenyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group (including substituted aryl groups) having 3 to 20 carbon atoms. Alternatively, the three groups are alkyl groups having 1 to 4 carbon groups, phenyl groups, naphthyl groups, or mixtures thereof. The three groups may be halogenated, for example fluorinated aryl groups. In yet other illustrative examples, the neutral stoichiometric activator is trisperfluorophenylboron or trisperfluoronaphthylboron.

The ionic stoichiometric activator compound may contain an active proton, or some other cation that is associated with, but not coordinated to, or only loosely coordinated to, the remaining ion of the ionizing compound. Such compounds are described, for example, in European publications EP-A-0570982, EP-A-0520732, EP-A-0495375, EP-B1-0500944, EP-A-0277003 and EP-A-0277004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124.

Carrier

The catalyst compounds described above may be combined with one or more supports using one of the support methods well known in the art or as described below. For example, the compound may be used in the catalyst in a supported form (e.g., deposited on, contacted with, incorporated within, adsorbed or absorbed in or on a support).

As used herein, the term "support" refers to compounds comprising group 2, group 3, group 4, group 5, group 13, and group 14 oxides and chlorides. Suitable supports include, for example, silica, magnesia, titania, zirconia, montmorillonite, phyllosilicate, alumina, silica-chromium, silica-titania, magnesium chloride, graphite, magnesia, titania, zirconia, montmorillonite, phyllosilicate, and the like.

The average particle size of the support may range from about 0.1 to about 500 μm, or from about 1 to about 200 μm, or from about 1 to about 50 μm, or from about 5 to about 50 μm.

The average pore size of the support is from about 10 to about

Or about 50 to about

Or 75 to about

Within the range.

The surface area of the support may be from about 10 to about 700m²In terms of/g, or from about 50 to about 500m²In terms of/g, or from about 100 to about 400m²In the range of/g.

The pore volume of the support is in the range of about 0.1 to about 4.0cc/g, or about 0.5 to about 3.5cc/g, or about 0.8 to about 3.0 cc/g.

The support (e.g., inorganic oxide) has a thickness of about 10 to about 700m²In the range of/gSurface area, pore volume in the range of about 0.1 to about 4.0cc/g, and average particle size in the range of about 1 to about 500 μm. Alternatively, the carrier may have about 50 to about 500m²A surface area in the range of/g, a pore volume of about 0.5 to about 3.5cc/g, and an average particle size of about 10 to about 200 μm. The surface area of the support may also be from about 100 to about 400m²In the/g range, the pore volume is from about 0.8 to about 3.0cc/g and the average particle size is from about 5 to about 100 μm.

The catalyst compound may be supported together with the activator on the same or a separate support, or the activator may be used in unsupported form, or may be deposited on a different support than the supported catalyst compound.

Various other methods exist in the art for supporting polymerization catalyst compounds. For example, the catalyst compound may contain a polymer-bound ligand, as described, for example, in U.S. patent nos. 5,473,202 and 5,770,755; the catalyst can be spray dried as described, for example, in U.S. Pat. No. 5,648,310; the support used with the catalyst may be functionalized as described in European publication EP-A-0802203; or at least one substituent or leaving group is selected as described in U.S. Pat. No. 5,688,880.

Supported catalyst compositions and methods of preparation

The supported catalyst compositions disclosed herein may comprise a porous particulate support as disclosed above, one or more catalyst compounds as disclosed above, and one or more activator compounds as disclosed above.

The one or more catalyst compounds may comprise titanium, zirconium or hafnium atoms. The catalyst compound may comprise:

(pentamethylcyclopentadienyl) (propylcyclopentadienyl) MX₂，

(Tetramethylcyclopentadienyl) (propylcyclopentadienyl) MX₂，

(Tetramethylcyclopentadienyl) (butylcyclopentadienyl) MX₂，

Me₂Si (indenyl)₂MX₂，

Me₂Si(tetrahydroindenyl)₂MX₂，

(n-propylcyclopentadienyl)₂MX₂，

(n-butylcyclopentadienyl)₂MX₂，

(1-methyl, 3-butylcyclopentadienyl)₂MX₂，

HN(CH₂CH₂N(2,4,6-Me₃Phenyl))₂MX₂，

HN(CH₂CH₂N(2,3,4,5,6-Me₅Phenyl))₂MX₂，

(propylcyclopentadienyl) (tetramethylcyclopentadienyl) MX₂，

(butylcyclopentadienyl)₂MX₂，

(propylcyclopentadienyl)₂MX₂And mixtures thereof,

The supported catalyst composition can comprise two or more catalyst compounds comprising titanium, zirconium, or hafnium atoms. The two or more catalyst compounds may comprise one or more metallocene compounds and one or more group 15 containing metal compounds. The metallocene compound may comprise

(pentamethylcyclopentadienyl) (propylcyclopentadienyl) MX₂，

(Tetramethylcyclopentadienyl) (propylcyclopentadienyl) MX₂，

(Tetramethylcyclopentadienyl) (butylcyclopentadienyl) MX₂，

Me₂Si (indenyl)₂MX₂，

Me₂Si (tetrahydroindenyl)₂MX₂，

(n-propylcyclopentadienyl)₂MX₂，

(n-butylcyclopentadienyl)₂MX₂，

(1-methyl, 3-butylcyclopentadienyl)₂MX₂，

(propylcyclopentadienyl) (tetramethylcyclopentadienyl) MX₂，

(butylcyclopentadienyl)₂MX₂，

(propylcyclopentadienyl)₂MX₂And mixtures thereof,

The group 15 metal-containing compound may comprise

HN(CH₂CH₂N(2,4,6-Me₃Phenyl))₂MX₂Or

HN(CH₂CH₂N(2,3,4,5,6-Me₅Phenyl))₂MX₂Wherein M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH₂SiMe₃And C₁To C₅An alkyl or alkenyl group.

The supported catalyst composition may comprise two catalyst compounds selected from:

(pentamethylcyclopentadienyl) (propylcyclopentadienyl) MX₂，

(Tetramethylcyclopentadienyl) (propylcyclopentadienyl) MX₂，

(Tetramethylcyclopentadienyl) (butylcyclopentadienyl) MX₂，

Me₂Si (indenyl)₂MX₂，

Me₂Si (tetrahydroindenyl)₂MX₂，

(n-propylcyclopentadienyl)₂MX₂，

(n-butylcyclopentadienyl)₂MX₂，

(1-methyl, 3-butylcyclopentadienyl)₂MX₂，

(propylcyclopentadienyl) (tetramethylcyclopentadienyl) MX₂，

(butylcyclopentadienyl)₂MX₂Or

(propylcyclopentadienyl)₂MX₂And

HN(CH₂CH₂N(2,4,6-Me₃phenyl))₂MX₂Or

HN(CH₂CH₂N(2,3,4,5,6-Me₅Phenyl))₂MX₂，

Wherein M is Zr or Hf and X is selected from the group consisting of: F. cl, Br, I, Me, benzyl, CH₂SiMe₃And C1 to C5 alkyl or alkenyl groups.

The supported catalyst composition may comprise a liquid diluent content of 7% or less, or 6% or less, or 5% or less, or 4% or less, or 3% or less. The supported catalyst composition can comprise a toluene content of 7% or less, or 6% or less, or 5% or less, or 4% or less, or 3% or less.

The supported catalyst composition can comprise porous particulate silica, methylaluminoxane, one or more catalyst compounds as described above, and a toluene content of 7% or less, or 6% or less, or 5% or less, or 4% or less, or 3% or less, based on the total weight of the supported catalyst composition.

A method of preparing a supported catalyst composition may involve forming a suspension of one or more porous particulate supports, one or more catalyst compounds, and one or more activator compounds in one or more liquid diluents, and then spray drying the suspension. The suspension may be formed by combining, blending, mixing, modifying, and the like.

The supported catalyst composition may be formed by combining one or more catalyst compounds with one or more activator compounds and then combining the resulting mixture with one or more porous particulate supports. The supported catalyst composition may be formed by combining one or more activator compounds with one or more porous particulate supports and then combining the resulting mixture with one or more catalyst compounds. The components may be combined in the presence of a liquid diluent. The diluent used to form the suspension may be a material capable of dissolving or suspending the catalyst compound and activator compound and suspending the porous particulate support. For example, hydrocarbons, such as straight or branched chain paraffins, including n-hexane, n-pentane, and isopentane; aromatic compounds such as toluene and xylene; and halogenated hydrocarbons, such as methylene chloride, are suitable as diluents. The diluent may have a boiling point of about 0 ℃ to about 150 ℃.

The same or different diluents can be used for the catalyst compound and the activator compound.

In one approach the activator may comprise an alumoxane, such as methylalumoxane or modified methylalumoxane. In one process the diluent may comprise toluene.

The contact time of the one or more activators with the one or more catalyst compounds may vary depending on one or more of the following conditions: temperature and pressure, type of mixing equipment, and amount of components to be combined.

The combination of the one or more activators with the one or more catalyst compounds can be carried out over a period of time of between about 1 minute and 2 hours.

After combining the one or more activators with the one or more catalyst compounds, the resulting mixture may be held for a period of time between about 1 minute and 2 hours. Alternatively, the resulting mixture may remain for up to three days after combining the one or more activators with the one or more catalyst compounds. The mixture may be maintained at a temperature of 10 ℃ to 100 ℃,10 ℃ to 50 ℃, or 15 ℃ to 35 ℃.

The mixture of activator compound and catalyst compound may then be added to the porous particulate support. The porous particulate carrier may be slurried in a suitable liquid diluent prior to addition. The liquid diluent may comprise toluene.

The combination of the mixture of one or more activators and one or more catalyst compounds with the one or more porous particulate supports may be carried out over a period of time of from about 1 minute to about 2 hours.

After combining the one or more activators, the one or more catalyst compounds, and the one or more porous particulate supports, the mixture may be held for a period of time between about 1 minute and 2 hours. Alternatively, the mixture may be maintained for up to three days after combining the one or more activators, the one or more catalyst compounds, and the one or more porous particulate supports. The mixture may be maintained at a temperature of 10 ℃ to 100 ℃,10 ℃ to 50 ℃, or 15 ℃ to 35 ℃.

The use of spray drying in the present disclosure includes the use of a large hot gas stream to rapidly evaporate the liquid diluent from the suspension, thereby forming the supported catalyst of the present disclosure. The suspension is fed into the drying chamber as a fine mist formed or "atomized" using a nozzle, rotating disc or wheel disc. The liquid diluent is evaporated in the drying chamber, which helps cool the drying gas and the supported catalyst of the present disclosure. The drying gas, vaporized diluent liquid, and supported catalyst are then transferred from the drying chamber to a particle separation unit, such as a cyclone or baghouse, where the supported catalyst is collected. The ratio of the flow rates of the hot gas and the diluent liquid, the temperatures of these two streams, and the physical properties of the diluent liquid (e.g., the heat of vaporization) help determine the temperature of the material as it exits the drying chamber. For example, for a production rate of 25kg/h at 35 ℃ to produce a supported catalyst composition from a suspension containing a total of 10 wt% dissolved plus suspended components, a nitrogen flow rate of 3500kg/h at 150 ℃ will produce a supported catalyst composition at a drying chamber outlet temperature of 80 ℃ to 120 ℃, where the exact temperature will depend on the specific identity of the components.

Thus, spray drying may be carried out by: the suspension is atomized into a stream of heated inert dry gas (such as nitrogen, argon or propane) with a nozzle or centrifugal high-speed disk atomizer to evaporate the diluent and produce solid-form particles of the supported catalyst and activator in the matrix of support material. The volumetric flow rate of the drying gas may be significantly greater than the volumetric flow rate of the suspension. Spray drying the suspension to form the supported catalyst composition includes verifying that the suspension has a residence time in the drying chamber of 5 seconds to 60 seconds. Alternatively, spray drying the suspension to form the supported catalyst composition comprises verifying that the suspension has a residence time in the drying chamber of 5 seconds to 45 seconds or a residence time of 5 seconds to 30 seconds.

The amount of catalyst compound and activator compound employed in the suspension of catalyst, activator, and support material may depend on the nature of the activator. When the activator is a branched or cyclic aluminoxane, the molar ratio of aluminum atoms (from the activator) to transition metal (from the catalyst compound) in the suspension can be between about 10 and about 5000, or between about 50 and about 1000, or between about 100 and about 500.

The amount of porous particulate support used to form the suspension can be from about 1 to about 80 wt%, or from about 10 to about 60 wt%, or from about 20 to about 50 wt%, based on the total weight of the supported catalyst composition.

The spray-dried supported catalyst composition may be a particulate material containing at least one activator compound and at least one catalyst compound in a matrix of at least one inert support material. The average particle size of the particles of the supported catalyst composition can be from 5 to 500, or from 10 to 80 microns.

The process for preparing a supported catalyst composition is characterized in that after forming a suspension comprising one or more porous particulate supports, one or more activator compounds and one or more catalyst compounds in one or more liquid diluents, the suspension is spray dried to form the supported catalyst composition. Wherein the weight of solids in the suspension is greater than 200kg and the time taken for the spray drying step is 10 hours or less. Wherein the weight of solids in the suspension is greater than 200kg, the time taken for spray drying may be 9 hours or less, or 8 hours or less, or 7 hours or less, or 6 hours or less, or 5 hours or less, or 4 hours or less, or 3 hours or less. The time may be between 2 hours and 10 hours, or between 2 hours and 8 hours.

The suspension may be spray dried such that the supported catalyst composition has a residual liquid content of 10 wt% or less, 7 wt% or less, or 5 wt% or less, or 4 wt% or less, or 3 wt% or less, or 2 wt% or less after spray drying. The suspension may be spray dried such that the toluene content of the supported catalyst composition after spray drying is 10 wt.% or less, 7 wt.% or less, or 5 wt.% or less, or 4 wt.% or less, or 3 wt.% or less, or 2 wt.% or less

The weight of solids in the suspension may be greater than 300kg, or greater than 400kg, or greater than 500 kg.

The weight% of the solids of the suspension in the liquid vehicle can be between about 5 weight% and about 60 weight%, or between about 10 weight% and about 50 weight%, or between about 20 weight% and about 40 weight%.

The suspension may be spray dried at a rate of between about 100kg/h and 1000kg/h or between about 200kg/h and about 800 kg/h. Suspension refers to a mixture of solids and diluent.

In one embodiment, the suspension of particulate silica, methylaluminoxane, and one or more catalyst compounds in a toluene liquid diluent can be spray dried at a rate sufficient to produce at least 200kg of supported catalyst composition in 10 hours or less and have a toluene content of 7 wt.% or less.

In another embodiment, a suspension of particulate silica, methylaluminoxane, and one or more catalyst compounds in a toluene liquid diluent can be spray dried at a rate sufficient to produce at least 300kg of supported catalyst composition in 10 hours or less and have a toluene content of 7 wt.% or less.

In another embodiment, a suspension of particulate silica, methylaluminoxane, and one or more catalyst compounds in a toluene liquid diluent can be spray dried at a rate sufficient to produce at least 400kg of supported catalyst composition in 10 hours or less and have a toluene content of 7 wt.% or less.

In another embodiment, a suspension of particulate silica, methylaluminoxane, and one or more catalyst compounds in a toluene liquid diluent can be spray dried at a rate sufficient to produce at least 500kg of supported catalyst composition in 10 hours or less and have a toluene content of 7 wt.% or less.

In any of the above embodiments, the suspension may be spray dried at a rate sufficient to produce a supported catalyst composition in 10 hours or less, and have a toluene content of 6 wt.% or less, or 5 wt.% or less, or 4 wt.% or less, or 3 wt.% or less.

In any of the above embodiments, the suspension may be spray dried at a rate sufficient to produce a supported catalyst composition in 7 hours or less, and have a toluene content of 6 wt.% or less, or 5 wt.% or less, or 4 wt.% or less, or 3 wt.% or less.

In any of the above embodiments, the suspension may be spray dried at a rate sufficient to produce a supported catalyst composition in 5 hours or less, and have a toluene content of 6 wt.% or less, or 5 wt.% or less, or 4 wt.% or less, or 3 wt.% or less.

In another embodiment, a suspension of particulate silica, methylaluminoxane, and one or more catalyst compounds in a toluene liquid diluent can be spray dried at a rate sufficient to produce at least 500kg of supported catalyst composition in 7 hours or less and have a toluene content of 4 wt.% or less.

The supported catalyst composition may be retained in a substantially dry and/or free-flowing form, or may be reslurried in a suitable liquid. The supported catalyst composition may be mixed with a suitable protective material, such as mineral oil, for storage.

Continuity additives/adjuvants

It may also be desirable to use one or more continuity additives to, for example, help regulate static levels in the polymerization reactor. The continuity additive may be used as part of the supported catalyst composition or introduced directly into the reactor independently of the supported catalyst composition. The continuity additive can be supported on the inorganic oxide of the supported catalyst composition described herein.

Non-limiting examples of continuity additives include amide-hydrocarbon or ethoxylated amide compounds, as described as "surface modifiers" in WO 96/11961; carboxylate compounds, such as aryl-carboxylates and long chain hydrocarbon carboxylates, and fatty acid-metal complexes; alcohols, ethers, sulfate compounds, metal oxides, and other compounds known in the art. Some specific examples of continuity additives include 1, 2-diether organic compounds, magnesium oxide, ARMOSTAT 310, ATMER 163, ATMER AS-990, and other glycerides, ethoxylated amines (e.g., N-bis (2-hydroxyethyl) octadecyl amine), alkyl sulfonates, and alkoxylated fatty acid esters; STADIS 450 and 425, KEROSTAT CE 4009 and KEROSTAT CE 5009 chromium N-oleyl anthranilate, calcium salt of Medialan acid, and di-tert-butylphenol; POLYFLO 130, TOLAD 511 (a-olefin-acrylonitrile copolymer and polymeric polyamine), EDENOL D32, aluminum stearate, sorbitan-monooleate, glycerol monostearate, methyl benzoate, dimethyl maleate, dimethyl fumarate, triethylamine, 3-diphenyl-3- (imidazol-1-yl) -propyne (propin), and the like.

Any of the foregoing additional continuity additives may be used alone or in combination.

Other continuity additives suitable for use in embodiments disclosed herein are well known to those of ordinary skill in the art. Regardless of which continuity additive is used, care should be taken to select an appropriate continuity additive to avoid introducing poisons into the reactor. Additionally, in selected embodiments, the minimum amount of continuity additive necessary to bring the static charge into the desired range should be used.

The continuity additive may be added to the reactor as a combination of two or more of the continuity additives listed above. The continuity additive may be added to the reactor in the form of a solution or slurry (e.g., a slurry with mineral oil) and may be added to the reactor as a separate feed stream or may be combined with other feeds prior to addition to the reactor. For example, the continuity additive may be combined with the supported catalyst or supported catalyst slurry prior to feeding the combined catalyst-static control agent mixture into the reactor.

The continuity additive may be added to the reactor in an amount ranging from about 0.05 to about 200ppmw, or from about 2 to about 100ppmw, or from about 2 to about 50ppmw, based on the polymer production rate. The continuity additive can also be added to the reactor in an amount of about 2ppmw or greater, based on the polymer production rate.

Process for using supported catalyst composition

Those skilled in the art recognize that depending on the olefin polymerization composition used, certain temperature and pressure conditions will be required to prevent, for example, loss of catalyst system activity.

The supported catalyst composition as disclosed above may be introduced directly into the polymerization reactor as a substantially dry powder. The catalyst may be in the form of a slurry in a suitable liquid.

It will be appreciated that the exact method of introduction may vary depending on one or more of the following conditions: temperature and pressure, type of mixing equipment, and amount of components to be combined.

Polymerization process

The polymerization process may include solution, gas phase, slurry phase, as well as high pressure processes or combinations thereof. In illustrative embodiments, a gas-phase or slurry-phase polymerization of one or more olefins (at least one of which is ethylene or propylene) is provided. The reactor may be a gas phase fluidized bed polymerization reactor.

The supported catalyst composition prepared by the process as described above is suitable for use in any prepolymerization and/or polymerization process over a wide range of temperatures and pressures. The temperature may be from-60 ℃ to about 280 ℃,50 ℃ to about 200 ℃; in the range of 60 ℃ to 120 ℃,70 ℃ to 100 ℃ or 80 ℃ to 95 ℃.

The olefin polymerization process may be a solution, high pressure, slurry or gas phase polymerization process of one or more olefin monomers having from 2 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and more preferably from 2 to 8 carbon atoms. The process is particularly well suited for the polymerization of two or more olefins or comonomers, such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and the like.

Other olefins suitable for use in the polymerization process include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers, and cyclic olefins. Suitable monomers may include, but are not limited to, norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene, and cyclopentene. In an illustrative embodiment of the process of the present invention, a copolymer of ethylene is made in which a comonomer having at least one alpha-olefin having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms, is polymerized with ethylene in a gas phase process. In another embodiment of the polymerization process, ethylene or propylene is polymerized with at least two different comonomers (optionally one of which can be a diene) to form a terpolymer.

The polymerization process may involve a polymerization process, particularly a gas or slurry phase process, for polymerizing propylene alone or with one or more other monomers including ethylene and/or other olefins having from 4 to 12 carbon atoms. The polymerization process can comprise contacting ethylene and optionally an alpha-olefin with one or more of the catalyst compositions described above in a reactor under polymerization conditions to produce an ethylene polymer or copolymer.

Suitable gas phase polymerization processes are described, for example, in U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661, 5,668,228, 5,627,242, 5,665,818 and 5,677,375, and European publications EP-A-0794200, EP-A-0802202, EP-A20891990 and EP-B-634421.

Slurry polymerization processes generally employ pressures in the range of from about 1 atmosphere to about 50 atmospheres and even higher, and temperatures in the range of from 0 ℃ to about 120 ℃. In slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and usually hydrogen and catalyst are added. The suspension comprising diluent is intermittently or continuously removed from the reactor, wherein the volatile components are separated from the polymer and recycled to the reactor, optionally after distillation. The liquid diluent used in the polymerization medium is generally an alkane having from 3 to 7 carbon atoms, preferably a paraffinic hydrocarbon. The medium employed should be liquid under the polymerization conditions and relatively inert. When a propane medium is used, the process must be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or isobutane medium is used.

The preferred polymerization process is referred to as particle form polymerization, or slurry process, wherein the temperature is maintained below the temperature at which the polymer becomes a solution. Such techniques are well known in the art and are described, for example, in U.S. Pat. No. 3,248,179. Other slurry processes include those using loop reactors and those using multiple stirred reactors in series, parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous loop or stirred tank processes. Additionally, other examples of slurry processes are described in U.S. Pat. No. 4,613,484. Examples of solution processes are described in U.S. Pat. nos. 4,271,060, 5,001,205, 5,236,998, and 5,589,555.

Examples of the invention

It should be understood that while the present disclosure has been described in conjunction with specific embodiments thereof, the foregoing description is intended to illustrate and not limit the scope of the disclosure. Other aspects, advantages, and modifications will be apparent to those skilled in the art to which the disclosure pertains. Thus, the following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the disclosed compositions, and are not intended to limit the scope of the disclosure.

For the sake of brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to recite a range not explicitly recited, and a range from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, and in the same manner, a range from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.

All cited documents are fully incorporated herein by reference for all jurisdictions in which such incorporation is permitted and to the extent such disclosure is consistent with the description of the present disclosure.

Preparation of spray-dried Supported catalyst compositions

To the stirred vessel were added toluene, and a 10 wt.% solution of methylalumoxane in toluene (jacobian, swallow, Louisiana, Albemarle Corporation, Baton Rouge, Louisiana). A25 wt.% solution of bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride (MCN) in toluene was then added. The mixture was held at 27 ℃ for one hour. A separate stirred vessel was charged with silica (Davison 948 or 955 grade silica available from graves (w.r. grace), Davison Chemical Division, Baltimore, Marylan) which was pre-dehydrated at 600 ℃. The methylaluminoxane/catalyst mixture was then added to the silica and the resulting mixture was stirred for one hour. A 10 wt% solution of antistatic agent (bis 2-hydroxyethyl stearamide) was added and allowed to mix for one hour. The catalyst suspension was transferred to a spray dryer agitator feeder and fed to the dryer. After steady state operation was reached, the product was collected. Table 1 shows the amount of starting material, spray drying conditions and catalyst analysis.

TABLE 1

Catalyst and process for preparing same		1	2	3	4
						Silicon dioxide	Type (B)	955	955	948	948
Weight of load
						Toluene	kg	11.5	11.4	11.3	11.3
10% MAO in toluene	kg	8.5	8.5	8.5	8.5
						Silicon dioxide	kg	2.3	2.3	2.3	2.3
25% MCN in toluene	g	245	245	245	245
						Containing a catalyst	wt％	14.6	14.6	14.6	14.6
Conditions of spray drying
						Inlet temperature	C	165.1	165.0	165.1	165.0
Outlet temperature	C	107.6	114.1	105.6	113.2
						Gas flow	kg/h	344	339	344	343
Flow of raw material	kg/h	49	34	49	40
						Speed of atomizer	RPM	21,600	21,600	21,600	21,600
Product collection	g	838	864	802	902
						Analysis of
Al	wt％	12.2	12.2	11.4	11.9
						Zr	wt％	0.45	0.46	0.4	0.43
Al/Zr	mol/mol	91.6	89.6	96.3	93.5
						Toluene	wt％	3.2	2.7	3.8	2.9
d₁₀	μ	8.8	9.9	17.9	19.9
						d₅₀	μ	39.7	39.3	49	49.6
d₉₀	μ	78.1	75.7	86.7	87.3

Preparation of the catalyst Using conventional drying

Catalyst I: to the stirred vessel were added 575kg of toluene and 481kg of a 30% by weight solution of methylalumoxane in toluene (Yao Bauhu, Louisiana), followed by flushing the line with 49kg of toluene. 42kg of a 25% by weight solution of bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride in toluene were then added, and the line was subsequently flushed twice with 49kg of toluene. The mixture was held at 27 ℃ for one hour. A separate stirred vessel was charged with 386kg of silica (Davison 948 silica, available from Grace, Devison chemical, Ballmo, Md.) which was pre-dehydrated at 600 ℃. The methylaluminoxane/catalyst mixture was then added to the silica and the transfer lines were flushed with 136kg of toluene and the resulting mixture was stirred for one hour. 27kg of a 10 wt% solution of antistatic agent (bis 2-hydroxyethyl stearamide) was added, followed by flushing the line with 49kg of toluene and allowing to mix for one hour. The supported catalyst was dried at 73.9 ℃ under a vacuum of 0.255 to 0.186 bar absolute with a nitrogen flow rate of 9.07 kg/h. The total drying time was 18 h.

Catalyst II: 760kg of toluene and 481kg of a 30% by weight solution of methylalumoxane in toluene (Yao Bay Co., Bargulu, Louisiana) were added to the stirred vessel, followed by flushing the line with 49kg of toluene. Then 42kg of a 25% by weight solution of dimethyl bis (n-propylcyclopentadienyl) hafnium (bis (n-propylcyclopentadienylhafnium dimethyl) in toluene were added, followed by flushing the line twice with 49kg of toluene. The mixture was held at 27 ℃ for one hour. 386kg of silica (PQ ES70 silica, available from PQ Corporation, Consheuchon, Pa.) dehydrated beforehand at 600 ℃ was added and the resulting mixture was stirred for one hour. The catalyst was dried at 73.9 ℃ under a vacuum of 0.255 to 0.186 bar absolute with a nitrogen flow rate of 9.07 kg/h. The total drying time was 18.6 h. The total amount of toluene added was 1275kg (69 wt% toluene). After drying for 5h, the supported catalyst contained about 51 wt% toluene. After 10 hours of drying, the supported catalyst contained about 22% toluene. Table 2 shows the amount of toluene recovered from the catalyst and the calculated toluene content of the catalyst and toluene mixture. A total of 1097kg of toluene was recovered from 1275kg of the added toluene. The remaining 178kg of toluene were contained in a nitrogen stream into a stirred vessel and left the process. The recovered toluene represents the total liquid condensed. When the concentration of toluene in the nitrogen sparge is below the dew point, no additional liquid toluene is recovered, but toluene is still released from the catalyst and exits the system. Thus, the results in table 2 represent the minimum amount of toluene in the process, as toluene leaving with the nitrogen is not included.

TABLE 2

Time (h)	Toluene recovery (kg)	Toluene content (wt%)
			1	53	65.9
2	158	63.5
			3	245	61.2
4	400	56.3
			5	540	50.7
6	659	44.8
			7	742	39.6
8	819	34.0
			9	882	28.4
10	946	21.8
			11	1,007	14.2
12	1,059	6.6
			13	1,085	2.1
14	1,094	0.4
			15	1,096	0.1

Laboratory polymerization test

A2 liter autoclave reactor was charged with 0.20 mmole of triisobutylaluminum TIBAL in hexane, followed by 1-hexene comonomer (60ml) and 800ml of isobutane diluent under a nitrogen purge. The reactor contents were heated to 80 ℃, after which about 50mg of the catalyst composition and 3mg of aluminum distearate were introduced while ethylene was added to the reactor to compensate for the total reactor pressure of 22.4 bar. The reactor temperature was maintained at 85 ℃ and the polymerization was allowed to proceed. After 90 minutes the reactor was cooled, ethylene and isobutane were vented, and the polymer was dried and weighed to obtain the yield. Table 3 compares the polymerization results of catalysts 1 to 4 prepared above and the control catalyst prepared with conventional vacuum drying.

TABLE 3

Pilot plant polymerization test

The supported catalysts prepared by spray drying and conventional drying were also tested in a continuous pilot scale gas phase fluidized bed reactor having an internal diameter of 0.6 meters and a bed height of 4.4 meters. The fluidized bed consists of polymer particles and a gaseous feed stream of ethylene and hydrogen is introduced into the recycle gas line below the reactor bed together with liquid 1-hexene comonomer. The individual flow rates of ethylene, hydrogen and 1-hexene were controlled to maintain fixed composition targets. The ethylene concentration was controlled to maintain a constant ethylene partial pressure. The hydrogen was controlled to maintain a constant hydrogen to ethylene molar ratio. The concentration of all gases was measured by on-line gas chromatography to ensure a relatively constant composition in the recycle gas stream. The reacting bed of growing polymer particles is maintained in a fluidized state by the continuous flow of make-up feed and recycle gas through the reaction zone. A superficial gas velocity of about 0.7 m/s was used to achieve this. The reactor was operated at a total pressure of 2200 kPa. The bed is maintained at a constant height by withdrawing a portion of the fluidized bed at a rate equal to the rate of formation of the granular product. The polymer production rate is in the range of 60-70 kg/hr. The product is removed semi-continuously through a series of valves into a fixed volume chamber. This product was purified to remove entrained hydrocarbons and treated with a small stream of moist nitrogen to deactivate any traces of residual catalyst.

Catalyst composition 4 prepared by the spray drying process of the present invention gave a productivity of 7,010kg polymer/kg catalyst and the catalyst composition prepared by conventional vacuum drying gave a productivity of 6,920kg polymer/kg catalyst. In addition, reactor shell temperature and static measurements indicate that the spray dried catalyst composition performs well without process interference.

Preparation of Large Scale spray-dried Supported catalyst compositions

To the stirred vessel were added 575kg of toluene and 481kg of a 30% by weight solution of methylalumoxane in toluene (Yao Bauhu, Louisiana), followed by flushing the line with 49kg of toluene. 42kg of a 25% by weight solution of bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride in toluene were then added, and the line was subsequently flushed twice with 49kg of toluene. The mixture was held at 27 ℃ for one hour. A separate stirred vessel was charged with 386kg of silica (Davison 948 silica, available from Grace, Devison chemical, Ballmo, Md.) which was pre-dehydrated at 600 ℃. The methylaluminoxane/catalyst mixture was then added to the silica and the transfer lines were flushed with 136kg of toluene and the resulting mixture was stirred for one hour. 27kg of a 10 wt% antistatic solution was added, followed by rinsing the lines with 49kg of toluene and allowing to mix for one hour. The catalyst suspension was transferred to a spray dryer agitator feeder and fed to the dryer at a 368kg/h feed rate at an atomizer speed of 21,600rpm at an inlet temperature of 165 ℃ and an outlet temperature of 113 ℃. 552kg of a supported catalyst composition catalyst was made with a zirconium content of about 0.4 wt% and an aluminum content of about 12.5 wt%. The supported catalyst composition was spray dried in about 5 hours.

Claims

1. A method of making a supported catalyst composition for olefin polymerization, comprising the steps of:

a) forming a suspension comprising one or more porous particulate supports, one or more activator compounds and one or more catalyst compounds in one or more liquid diluents, wherein step a) is performed in 5 hours or less; and

b) spray drying the suspension to form a supported catalyst composition;

wherein step b) is performed at a rate sufficient to produce at least 200kg of the supported catalyst composition in 5 hours or less.

2. The process of claim 1, wherein the residual liquid content of the supported catalyst composition after spray drying is 10 wt% or less, or 7 wt% or less, or 5 wt% or less, or 4 wt% or less, or 3 wt% or less, or 2 wt% or less.

3. The process of claim 1, wherein the weight% of the solids of the suspension in the liquid diluent is between 5 and 60 weight%, or between 10 and 50 weight%, or between 20 and 40 weight%, wherein the porous particulate support comprises (i) particulate group 2, group 3, group 4, group 5, group 13, and group 14 oxides or chlorides; or (ii) particulate silica, and wherein the suspension is spray dried at a rate between 100kg/h and 1000kg/h or between 200kg/h and 800 kg/h.

4. The process of claim 2, wherein the weight% of the solids of the suspension in the liquid diluent is between 5 and 60 weight%, or between 10 and 50 weight%, or between 20 and 40 weight%, wherein the porous particulate support comprises (i) particulate group 2, group 3, group 4, group 5, group 13, and group 14 oxides or chlorides; or (ii) particulate silica, and wherein the suspension is spray dried at a rate between 100kg/h and 1000kg/h or between 200kg/h and 800 kg/h.

5. The process of any one of claims 1 to 4, wherein the porous particulate support is dehydrated at an elevated temperature, and wherein the porous particulate support has an average particle size in the range of from 0.1 to 500 μm, or from 1 to 200 μm, or from 1 to 50 μm, or from 5 to 50 μm.

6. A process according to any one of claims 1 to 4, wherein the one or more activator compounds comprise an organometallic compound, an alumoxane or a neutral or ionic stoichiometric activator or a methylalumoxane or a modified methylalumoxane.

7. The process of any one of claims 1 to 4, wherein the liquid diluent comprises (i) an aliphatic or aromatic hydrocarbon or (ii) toluene, and wherein the one or more catalyst compounds comprise a titanium, zirconium, or hafnium atom.

8. The process of any one of claims 1 to 4, wherein a suspension of particulate silica, methylaluminoxane, and one or more catalyst compounds in a toluene liquid diluent is spray dried at a rate sufficient to produce at least 200kg of a supported catalyst composition in 5 hours or less and has a toluene content of 7 wt.% or less, wherein spray drying the suspension to form the supported catalyst composition comprises verifying a residence time of the suspension in a drying chamber of 5 seconds to 60 seconds.

9. The process of any one of claims 1 to 4, wherein step b) is carried out at an inlet temperature of 165 ℃.